Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

Handle URI:
http://hdl.handle.net/10754/563925
Title:
Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore
Authors:
Goswami, Subhadip; Winkel, Russell W.; Alarousu, Erkki; Ghiviriga, Ion; Mohammed, Omar F. ( 0000-0001-8500-1130 ) ; Schanze, Kirk S.
Abstract:
A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).
KAUST Department:
Solar and Photovoltaic Engineering Research Center (SPERC); Chemical Science Program; Physical Sciences and Engineering (PSE) Division
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry A
Issue Date:
18-Dec-2014
DOI:
10.1021/jp509987p
Type:
Article
ISSN:
10895639
Sponsors:
This work was supported by the National Science Foundation (Grant No. CHE-1151624). The ultrafast spectroscopy was carried out with support from the King Abdullah University of Science and Technology.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Solar Center (KSC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGoswami, Subhadipen
dc.contributor.authorWinkel, Russell W.en
dc.contributor.authorAlarousu, Erkkien
dc.contributor.authorGhiviriga, Ionen
dc.contributor.authorMohammed, Omar F.en
dc.contributor.authorSchanze, Kirk S.en
dc.date.accessioned2015-08-03T12:19:45Zen
dc.date.available2015-08-03T12:19:45Zen
dc.date.issued2014-12-18en
dc.identifier.issn10895639en
dc.identifier.doi10.1021/jp509987pen
dc.identifier.urihttp://hdl.handle.net/10754/563925en
dc.description.abstractA pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).en
dc.description.sponsorshipThis work was supported by the National Science Foundation (Grant No. CHE-1151624). The ultrafast spectroscopy was carried out with support from the King Abdullah University of Science and Technology.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titlePhotophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophoreen
dc.typeArticleen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Physical Chemistry Aen
dc.contributor.institutionDepartment of Chemistry, University of Florida, P.O. Box 117200Gainesville, FL, United Statesen
kaust.authorAlarousu, Erkkien
kaust.authorMohammed, Omar F.en
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